CN112979414B - Method for preparing aromatic compound from lignin - Google Patents
Method for preparing aromatic compound from lignin Download PDFInfo
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- CN112979414B CN112979414B CN201911282420.2A CN201911282420A CN112979414B CN 112979414 B CN112979414 B CN 112979414B CN 201911282420 A CN201911282420 A CN 201911282420A CN 112979414 B CN112979414 B CN 112979414B
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- lignin
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- organic polymer
- porous organic
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- 229920005610 lignin Polymers 0.000 title claims abstract description 31
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229920000620 organic polymer Polymers 0.000 claims abstract description 35
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 30
- 239000002585 base Substances 0.000 claims abstract description 23
- 230000035484 reaction time Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 claims 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 29
- 235000010333 potassium nitrate Nutrition 0.000 description 18
- 239000004323 potassium nitrate Substances 0.000 description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic nitrile Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 229920006391 phthalonitrile polymer Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UJXAVMZSVIODSH-UHFFFAOYSA-N 2-methylbenzene-1,4-dicarbonitrile Chemical compound CC1=CC(C#N)=CC=C1C#N UJXAVMZSVIODSH-UHFFFAOYSA-N 0.000 description 1
- OFCTVAYVCDCQDA-UHFFFAOYSA-N 2-phenylpropanedinitrile Chemical compound N#CC(C#N)C1=CC=CC=C1 OFCTVAYVCDCQDA-UHFFFAOYSA-N 0.000 description 1
- 101000713585 Homo sapiens Tubulin beta-4A chain Proteins 0.000 description 1
- 102100036788 Tubulin beta-4A chain Human genes 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B01J35/643—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The application discloses a method for preparing aromatic compounds by lignin, which at least comprises the following steps: in an oxygen atmosphere, a raw material containing lignin is in contact reaction with a solid base catalyst to obtain an aromatic compound; the solid base catalyst comprises a nitrogen-containing porous organic polymer and an alkali metal oxide, wherein the alkali metal oxide is supported on the nitrogen-containing porous organic polymer. According to the method for preparing the aromatic compound from the lignin, the lignin can be cracked at high selectivity under mild conditions to obtain the aromatic compound, and the solid base catalyst used in the reaction is fully contacted with the raw material, so that the conversion rate and the selectivity are high in the reaction time period.
Description
Technical Field
The application relates to a method for preparing aromatic compounds from lignin, and belongs to the technical field of chemistry and chemical engineering.
Background
Aromatic compounds are important chemical raw materials, are widely applied to industries such as medicines, polyesters, plastics, cosmetics and the like, and are derived from the petrochemical industry in the traditional synthetic route. Lignin is an important component of the lignocellulosic biomass that can be regenerated, accounting for 15-30 wt% of its total amount. Considering that lignin has a unique aromatic structure, efficient conversion of lignin to aromatic compounds allows for the production of high value-added chemicals. However, lignin is an amorphous highly cross-linked macromolecule, and is mainly connected by C-C bonds and C-O bonds through complex connection modes such as beta-O-4, beta-5, beta-beta, beta-1, alpha-O-4 and the like, and the complex connection modes cause the difficulty in breaking the bonds. It is a necessary direction to develop a high-efficiency catalytic system for catalytically cracking lignin.
Current research approaches to lignin depolymerization include solvolysis, pyrolysis, reduction, oxidation, and the like, with base-catalyzed depolymerization (BCD) being an important depolymerization strategy. However, BCD processes typically use metered amounts of base, and are harsh with pyrolysis temperatures in the range of 270 ℃ to 330 ℃ with higher pressures.
Disclosure of Invention
According to one aspect of the application, a method for preparing aromatic compounds from lignin is provided, the lignin can be cracked to obtain aromatic compounds with high selectivity under mild conditions, and a solid base catalyst used in the application is fully contacted with a raw material, so that the conversion rate and the selectivity are high in a reaction time period. Compared with the traditional alkali catalytic depolymerization process, the method has the advantages of less alkali consumption, mild conditions, long service life of the catalyst and easy recovery.
The present application provides a method for producing aromatic compounds from lignin, said method comprising at least: in an oxygen atmosphere, a raw material containing lignin is in contact reaction with a solid base catalyst to obtain an aromatic compound; the solid base catalyst comprises a nitrogen-containing porous organic polymer and an alkali metal oxide, wherein the alkali metal oxide is supported on the nitrogen-containing porous organic polymer.
The solid base catalyst provided herein is a nitrogen-containing porous organic polymer containing basic sites that can be introduced by reductive decomposition of nitrates.
The nitrogen-containing porous organic polymer is generated by high-temperature self-polymerization of aromatic nitrile monomers.
Optionally, the lignin comprises 2-phenoxy-1-acetophenone.
Optionally, the aromatic compound comprises at least one of phenol, benzoic acid, methyl benzoate, methyl benzoylformate.
Optionally, the reaction conditions are: the reaction temperature is 100-180 ℃; the reaction time is 2-12 h; the reaction pressure is 1.0-6.0 MPa.
Optionally, the upper limit of the reaction temperature is selected from 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃, 120 ℃, 110 ℃, and the lower limit of the reaction temperature is selected from 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃.
Optionally, the upper limit of the reaction time is selected from 12h, 10h, 8h, 6h and 4h, and the lower limit is selected from 2h, 4h, 6h, 8h and 10 h.
Alternatively, the upper limit of the reaction pressure is selected from 6.0MPa, 5.5MPa, 5.0MPa, 4.5MPa, 4.0MPa, 3.5MPa, 3.0MPa, 2.5MPa, 2.0MPa, 1.5MPa and the lower limit is selected from 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa, 5.5 MPa.
Optionally, the molar ratio of the solid base catalyst to the lignin is 1: 5-1: 40.
optionally, the upper limit of the molar ratio of the solid base catalyst to the lignin is selected from 1: 40. 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, with the lower limit selected from 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1: 35.
Optionally, the alkali metal oxide comprises any one of lithium oxide, sodium oxide, potassium oxide, cesium oxide.
Optionally, the nitrogen-containing porous organic polymer comprises a triazine skeleton structural unit with a structural formula shown as a formula I;
wherein R is1，R2，R3Independently selected from phenylene, group with structure shown in formula I-2, and alkyl substituted phenylene;
wherein the alkyl group is selected from methyl or ethyl;
preferably, said R is1，R2，R3Independently selected from one of p-phenylene, o-phenylene, a group with a structure shown in a formula I-2, a group with a structure shown in a formula I-3-1 and a group with a structure shown in a formula I-3-2;
r is selected from methyl or ethyl;
preferably, said R is1，R2，R3The same is true.
Specifically, the preparation method of the polymer with the triazine skeleton structural unit comprises the following steps: adding a monomer and a catalyst into a high-temperature-resistant vacuum-sealed quartz tube, heating the quartz tube in a muffle furnace to perform polymerization reaction, removing impurities from the obtained solid through dilute hydrochloric acid after the reaction is finished, and then drying the solid in a vacuum oven to obtain the polymer with the triazine skeleton structural unit.
Optionally, the monomer comprises at least one of terephthalonitrile, phthalonitrile, trimenitrile, dicyanotoluene.
Alternatively, the catalyst used in the process for preparing a polymer having a triazine structural unit is zinc chloride.
Alternatively, in the method for preparing the polymer with the triazine skeleton structural unit, the molar ratio of the monomer to the catalyst is 1: 1-1: 10.
preferably, the monomer to catalyst molar ratio is 1: 1.
optionally, in the method for preparing the polymer with the triazine skeleton structural unit, the reaction temperature of the heating polymerization reaction is 300-600 ℃.
Preferably, the reaction temperature of the heating polymerization reaction is 400 ℃; the reaction time of the heating polymerization reaction is 30-60 h.
Further preferably, the reaction time of the heating polymerization reaction is 40 h.
Alternatively, the solid base catalyst is prepared by the following method: and mixing the prepared nitrogen-containing porous organic polymer with a nitrate solution, stirring for 24 hours at room temperature, evaporating to remove water, and drying to obtain the nitrogen-containing porous organic polymer loaded with potassium nitrate. And then uniformly adding the prepared porous organic polymer loaded with the nitrate into a high-temperature and high-pressure resistant tubular furnace, roasting in a nitrogen atmosphere, and obtaining the solid base catalyst after roasting.
Optionally, the mass percentage of the nitrate in the nitrogen-containing porous organic polymer loaded with potassium nitrate is 5-40%.
Preferably, the mass percentage of the nitrate in the nitrogen-containing porous organic polymer loaded with potassium nitrate is 20%.
Optionally, the roasting temperature is 300-600 ℃, and the roasting time is 0.5-2 h.
Further preferably, the calcination temperature is 400 ℃ and the calcination time is 1 hour.
Optionally, the nitrogen-containing porous organic polymer has ordered micropores, and the pore diameter of the micropores is 0.98-1.06 nm.
Optionally, the raw material further contains a solvent, and the solvent comprises at least one of methanol, ethanol, acetonitrile and cyclohexane.
Alternatively, the reaction is carried out in an autoclave.
The beneficial effects that this application can produce include:
according to the method for preparing the aromatic compound by using the lignin, the catalyst is a solid base catalyst, and the catalyst is high in efficiency, high in selectivity, reusable and good in performance.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
The conversion of 2-phenoxy-1-acetophenone (the remaining mole of 2-phenoxy-1-acetophenone)/(mole of 2-phenoxy-1-acetophenone) was 100%;
the aromatics selectivity (aromatics yield)/(2-phenoxy-1-acetophenone conversion) was 100%.
EXAMPLE 1 preparation of Nitrogen-containing porous organic Polymer A
Respectively adding 1g of terephthalonitrile and 1g of zinc chloride into a high-temperature resistant quartz tube, sealing the tube in vacuum, putting the tube into a muffle furnace for reaction at the reaction temperature of 400 ℃ for 40h, washing the obtained solid by dilute hydrochloric acid after natural cooling to remove the zinc chloride, and then drying the solid in a vacuum oven at the temperature of 80 ℃ for 12h to obtain the nitrogenous porous organic polymer A.
EXAMPLE 2 preparation of Nitrogen-containing porous organic Polymer B
Respectively adding 0.7g of 2, 5-dicyano toluene and 0.7g of zinc chloride into a high-temperature resistant quartz tube, sealing the tube in vacuum, putting the tube into a muffle furnace for reaction at the reaction temperature of 400 ℃ for 40h, washing the obtained solid by dilute hydrochloric acid after natural cooling to remove the zinc chloride, and then putting the solid in a vacuum oven for drying for 12h at the temperature of 80 ℃ to obtain the nitrogen-containing porous organic polymer B.
EXAMPLE 3 preparation of Nitrogen-containing porous organic Polymer C
1.0g of phthalonitrile and 1g of zinc chloride are respectively added into a high-temperature resistant quartz tube, the tube is sealed in a vacuum mode and then placed into a muffle furnace for reaction, the reaction temperature is 400 ℃, the reaction time is 40 hours, after natural cooling, the zinc chloride is removed from the obtained solid through dilute hydrochloric acid washing, and then the solid is placed into a vacuum oven for drying for 12 hours at the temperature of 80 ℃, so that the nitrogen-containing porous organic polymer C can be obtained.
EXAMPLE 4 preparation of Nitrogen-containing porous organic Polymer D
The preparation of sample D, which differs from the preparation of a, is that: the reaction temperature is 300 ℃ and the reaction time is 60 h.
EXAMPLE 5 preparation of Nitrogen-containing porous organic Polymer E
The preparation of sample E, which differs from the preparation of a, was: the reaction temperature is 600 ℃, and the reaction time is 30 h.
Example 6 preparation of catalyst # 1
0.9g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.1g of potassium nitrate and stirred for 24h at room temperature, and the potassium nitrate with the load of 10 percent can be obtained after evaporation to remove water and drying. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain the solid base catalyst No. 1, wherein in the sample No. 1, potassium oxide is supported on the nitrogen-containing porous organic polymer A.
Example 7 preparation of catalyst # 2
0.8g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.2g of potassium nitrate and stirred for 24h at room temperature, and the potassium nitrate with the load of 20 percent can be obtained after evaporation, dehydration and drying. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain a solid base catalyst No. 2, wherein in the sample No. 2, potassium oxide is supported on the nitrogen-containing porous organic polymer A.
Example 8 preparation of catalyst # 3
0.7g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.3g of potassium nitrate and stirred for 24h at room temperature, and the potassium nitrate with the load of 30 percent can be obtained after evaporation, dehydration and drying. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain a solid base catalyst No. 3, wherein in the sample No. 3, potassium oxide is supported on the nitrogen-containing porous organic polymer A.
Example 9 preparation of catalyst # 4
0.8g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.2g of lithium nitrate, stirred for 24h at room temperature, evaporated to remove water and dried to obtain 40% loaded potassium nitrate. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain a solid base catalyst No. 4, wherein in the sample No. 4, lithium oxide is supported on the nitrogen-containing porous organic polymer A.
Example 10 preparation of catalyst # 5
0.8g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.2g of sodium nitrate and stirred for 24h at room temperature, and the potassium nitrate with the load of 40% can be obtained after evaporation, dehydration and drying. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain a solid base catalyst No. 5, wherein in the sample No. 5, sodium oxide is supported on the nitrogen-containing porous organic polymer A.
EXAMPLE 11 preparation of catalyst # 6
0.8g of porous ordered polymer carrier A is added into 15mL of aqueous solution containing 0.2g of cesium nitrate, stirred for 24h at room temperature, evaporated to remove water and dried to obtain 40% loaded potassium nitrate. And uniformly adding supported potassium nitrate into a high-temperature-resistant tube furnace, roasting in a nitrogen atmosphere at the roasting temperature of 400 ℃ for 1h to obtain a solid base catalyst No. 6, wherein in the sample No. 6, cesium oxide is supported on the nitrogen-containing porous organic polymer A.
Example 12 preparation of catalyst # 7
The preparation of catalyst # 7, which differs from the preparation of catalyst # 2 in that: the nitrogen-containing porous organic polymer was changed to B.
EXAMPLE 13 preparation of catalyst # 8
The preparation of catalyst # 8, which differs from the preparation of catalyst # 2 in that: the nitrogen-containing porous organic polymer was changed to C.
Example 14 preparation of catalyst # 9
The preparation of catalyst # 9, which differs from the preparation of catalyst # 2 in that: the nitrogen-containing porous organic polymer was changed to D.
EXAMPLE 15 preparation of catalyst No. 10
The preparation of catalyst # 10, which differs from the preparation of catalyst # 2 in that: the nitrogen-containing porous organic polymer was changed to E.
Examples 16-29 testing of catalytic Performance of catalysts
The test method comprises the following steps: 848mg of 2-phenoxy-1-acetophenone, 200mg of solid base catalyst and 20mL of methanol as a solvent are added into a 60mL high-pressure reaction kettle, the oxygen pressure is 1.0MPa, and the reaction is carried out for 8 hours.
And (3) testing results: the substrate conversion and the selectivity for each aromatic compound after the reaction was completed were analyzed by GC.
Examples 16 to 29 are reactions carried out using different catalysts and temperatures, and specific catalysts and reaction temperatures are shown in table 1, in which the conversion rate of 2-phenoxy-1-acetophenone and the selectivity of each aromatic compound are also shown, and it can be seen from table 1 that the catalysts prepared by the preparation method of the present application have good catalytic efficiency for the reaction of lignin to aromatic compounds.
TABLE 1 catalysts, reaction temperatures and reaction results used in examples 16 to 29
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (6)
1. A method for producing aromatic compounds from lignin, characterized in that it comprises at least: in an oxygen atmosphere, a raw material containing lignin is in contact reaction with a solid base catalyst to obtain an aromatic compound;
the solid base catalyst comprises a nitrogen-containing porous organic polymer and an alkali metal oxide, wherein the alkali metal oxide is supported on the nitrogen-containing porous organic polymer;
the lignin comprises 2-phenoxy-1-acetophenone;
the aromatic compound comprises at least one of phenol, benzoic acid, methyl benzoate and methyl benzoylformate;
the alkali metal oxide comprises any one of lithium oxide, sodium oxide, potassium oxide and cesium oxide;
the nitrogen-containing porous organic polymer comprises a triazine skeleton structural unit with a structural formula shown as a formula I;
wherein R is1，R2，R3Independently selected from phenylene, group with structure shown in formula I-2, and alkyl substituted phenylene;
wherein the phenylene group is selected from p-phenylene or o-phenylene;
the alkyl substituted phenylene is selected from a group with a structure shown in a formula I-3-1 and a group with a structure shown in a formula I-3-2;
r is selected from methyl or ethyl.
2. The method for preparing aromatic compounds from lignin according to claim 1, wherein the reaction conditions are as follows: the reaction temperature is 100-180 ℃; the reaction time is 2-12 h; the reaction pressure is 1.0-6.0 MPa.
3. The method for preparing aromatic compounds from lignin according to claim 1, wherein the molar ratio of the solid base catalyst to the lignin is 1: 5-1: 40.
4. the method for preparing the aromatic compound by the lignin according to claim 1, wherein the nitrogen-containing porous organic polymer has ordered micropores, and the pore diameter of the micropores is 0.98-1.06 nm.
5. The method for preparing aromatic compounds from lignin according to claim 1, wherein the raw material further comprises a solvent, and the solvent comprises at least one of methanol, ethanol, acetonitrile and cyclohexane.
6. The method for preparing aromatic compounds from lignin according to claim 1, wherein the reaction is carried out in a reaction kettle.
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